1. Field of the Invention
The present invention relates broadly to nitrocellulose based coating compositions and is more particularly directed to such coating compositions possessed of low concentrations of Volatile Organic Compounds (hereinafter, xe2x80x9cVOCxe2x80x9d).
In the field of industrial finishing, particularly wood finishing, it is highly desirable that the coating compositions employed be rapidly curable to the finished state, thereby to minimize the time and expense required to produce finished coatings on the product to which the coating is applied. Industrial wood finishing involves protective coatings for such diverse products as furniture, cabinetry, joinery, millwork, flooring and miscellaneous coatings such as pencil lacquers, tool handle finishes, finishes for baseball bats and gun stocks. Traditional polymer based coating compositions are generally possessed of one or more detrimental characteristics which mitigate against their use in industrial finishing operations. Nitrocellulose lacquers are normally high in VOC and Hazardous Air Polluting Substances (hereinafter, xe2x80x9cHAPSxe2x80x9d) and are often slow to dry. Acid catalyzed nitrocellulose coating compositions are normally high in VOC and HAPS and, moreover, have finite pot lives requiring that the catalyzed batches thereof be entirely used within the alloted pot life. Alkyd urea compositions require heating and are generally slow to cure. Two part polyurethanes have finite pot lives and, while the coatings thereof are generally tough, they are often poor in sandability. Cellulose acetate butyrate compositions exhibit relatively low performance as protective coatings and, moreover, are high in VOC and HAPS. Oil modified polyurethanes are generally slow to cure and, in addition, often display relatively poor color properties. Moisture cured uralkyd coating compositions are slow to cure and are high in VOC. Acrylic coating compositions, which can be either solvent based or waterborne, generally provide finished coatings which, while sandable, are usually not tough and have poor resistance to scratching. When of the solvent based type, acrylic coating compositions also have high concentrations of VOC. Waterborne acrylic coatings are generally slow to dry, have limited aesthetic properties and tend to rust ferrous metal surfaces or to raise the fibers of wooden surfaces to which they are applied. Energy cured coating compositions, such as ultraviolet light or electron beam cured compositions have become more common in some industrial finishing markets. However, they, too, suffer from some limitations. For instance, urethane-acrylate compositions generally result in coatings which have relatively poor aesthetics and which have only poor to fair sandability. Epoxy coatings can display poor color characteristics and tend to yellow over time. Ultraviolet light cured acrylic coatings are not scratch resistant and have high shrinkage, thereby leading to poor adhesion to the substrate and facile crack propagation once the coated film is damaged. Acrylated urethanes can be employed to increase the toughness of acrylic coatings. However, the resulting coated films have poor sandability and hardness. Energy cured waterbased coatings must be dried prior to curing and, moreover, are possessed of the same rusting and fiber raising deficiencies mentioned above.
2. Description of Related Art
U.S. Pat. No. 5,496,589, Igarashi et al., issued Mar. 5, 1996 and assigned to Toagosei Chemical Industry Co., Ltd., discloses a radiation curable wood impregnant composition. This composition is made using long alkyloxy chains on methacrylates and is cured using ultraviolet (UV) or electron beam (EB) radiation. The cured impregnant composition is said to cure to a hardness of only about 4H.
U.S. Pat. No. 4,855,184, Klun et al., issued Aug. 8, 1989 and assigned to Minnesota Mining and Manufacturing Company, discloses a radiation curable protective coating composition which is applied in a solution of 40% butyl acetate, 20% propyl acetate and 20% n-propanol. Thus, the VOC concentration of the composition is high.
U.S. Pat. No. 4,565,857, R. J. Grant, issued Jan. 21, 1986 and assigned to Minnesota Mining and Manufacturing Company, discloses a radiation curable protective coating composition whose resinous content is comprised of cellulosic materials which are treated with isocyanatoethylmethacrylate in order to confer radiation curability thereto. The resin is coated onto a surface as a solution in organic solvents. Thus, the VOC concentration of the composition is high.
U.S. Pat. No. 6,057,033, W. L. Bilodeau, issued May 2, 2000 and assigned to Avery Dennison Corporation, discloses the use of cellulosic fibers and polyorganosilanes in the preparation of radiation curable release coating compositions. The resulting compositions are, therefore, low-surface energy coatings and their adhesion to substrates is inadequate to serve as protective coatings for the substrate.
It is a principal object of the invention to provide novel nitrocellulose based coating compositions.
It is another object of the invention to provide nitrocellulose based coating compositions having low VOC concentrations.
It is yet another object of the invention to provide nitrocellulose based coating compositions whose applied films are rapidly curable to the finished state.
It is still another object of the invention to provide nitrocellulose based coating compositions whose cured applied films have good adhesion and surface hardness properties.
It is another object of the invention to provide nitrocellulose based coating compositions whose cured applied films have good aesthetic and protective qualities.
It is another object of the invention to provide novel protective films formed from the nitrocellulose based coating compositions hereof.
Other objects and advantages of the present invention will, in part, be obvious and will, in part appear hereinafter.
The coating compositions of the invention broadly comprise the following four components: nitrocellulose, a polymerizable reactive diluent whose homopolymers have a glass transition temperature of less than 25xc2x0 C.; a polymerizable reactive diluent whose homopolymers have a glass transition temperature of greater than 25xc2x0 C. and an acrylated urethane. The compositions of the invention comprise between about 3 and about 25 percent by weight of the nitrocellulose component; between about 10 and about 50 percent by weight of the polymerizable reactive diluent component whose homopolymers have a glass transition temperature of less than 25xc2x0 C.; between about 25 and about 75 percent by weight of the polymerizable reactive diluent component whose homopolymers have a glass transition temperature of greater than 25xc2x0 C and between about 5 and about 40 percent by weight of the acrylated urethane component. The compositions of the invention may also include between about 0.5 and about 5 percent by weight of thermal and/or photoinitiators and up to about 5 percent by weight of conventional coating composition additives. The protective films of the invention comprise the cured reaction products of the foregoing compositions.
Nitrocellulose is the product of nitration of the hydroxyl groups on natural cellulose fibers. Preferably, in the practice of the present invention the nitrocellulose component utilized will be from about 10% to about 12.5% nitrated, thereby to maximize solubility of the nitrocellulose component in the reactive diluent components. The viscosity of the nitrocellulose component can reside within the range of commercially available nitrocellulose materials. The viscosity of nitrocellulose is conventionally provided in seconds and is tested in accordance with the standard method of ASTM Specification D301-50. Highly viscous nitrocellulose materials have viscosities within the range of about 30 and about 50 seconds while low viscosity materials have viscosities of less than one second. We generally prefer that the nitrocellose component of the compositions of the present invention have a viscosity of less than about 20 seconds and, of even greater preference, of less than about 1 second.
Because dry nitrocellulose is a highly flammable powder it is conventionally sold xe2x80x9cwetxe2x80x9d with a liquid in order to prevent dusting. Generally speaking, the wetting liquids commericially employed are water, isopropanol, ethanol and butanol. Other liquids, such as plasticizers, can also be utilized as the wetting liquid. Accordingly, it should be noted and understood that, for purposes of the present invention, the weight percentages of the nitrocellulose component spoken of herein refer to the commercially available xe2x80x9cwetxe2x80x9d nitrocellulose materials and not to the dry powder. Nitrocellulose materials suitable for use in the present invention are currently available from such sources as: Hegadorn, Osnabruck, Germany; ICI, Wilmington, Del.; Bayer, Wolfsrude, Germany; Bergerac NC, Bergerac, France and Green Tree, Parlin, N.J.
Reactive diluents utilized in the compositions of the present invention are typically monomeric compounds polymerizable by free radical reactions. They may be monofunctional, difunctional, trifunctional or have four or more reactive sites. As previously mentioned the reactive diluents of the invention are divided into two classes, those whose homopolymers have a glass transition temperature, Tg, of greater than 25xc2x0 C. and those whose homopolymers have a Tg of less than 25xc2x0 C. Glass transition temperatures are typically measured by differential scanning calorimetry and are indicated by a change in the amount of energy necessary to increase the temperature of the polymer sample by 1xc2x0 C. This change is typically attributed to the onset of motion within the polymer chain. The amounts of the reactive diluents employed in the nitrocellulose coating compositions of the invention are balanced to yield good coating properties in the cured films. For example, the amount of xe2x80x9chardxe2x80x9d or high Tg reactive diluent is sufficient to yield good scratch and abrasion resistance while the amount of xe2x80x9csoftxe2x80x9d or low Tg reactive diluent is sufficient to provide the cured film with good adhesion to the substrate. Thus, once the specific components of a proposed coating composition within the scope of the invention have been chosen, precise balancing of the amounts of reactive diluents employed to optimize coating properties can be readily achieved experimentally.
Exemplary suitable reactive diluents for use in the invention are as follows (numbers in parentheses represent number of repeat units).
Monofunctional
Butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, octyl acrylate, decyl acrylate, octyl/decyl acrylate blends, tridecyl acrylate, caprolactone acrylate, ethoxylated nonyl phenol acrylate, propoxylated allyl methacrylate, methoxy poly(ethylene glycol)(350) monomethacrylate, methoxy poly(ethylene glycol)(550)monomethacrylate, ethoxylated hydroxyethyl methacrylate, poly(propylene glycol) monomethacrylate, alkoxylated tetrahydrofurfuryl acrylate, beta-carboxyethyl acrylate.
Difunctional
Tri(ethylene glycol) dimethacrylate, tetra(ethylene glycol) dimethacrylate, poly(ethylene glycol) dimethacrylate, poly(ethylene glycol)(600)dimethacrylate, poly(ethylene glycol)(200)dimethacrylate, tetra(ethylene glycol) diacrylate, polyethylene glycol(400)diacrylate, ethoxylated(10)bisphenol-A dimethacrylate, alkoxylated hexandiol diacrylate (HDODA), alkoxylated cyclohexane dimethanol diacrylate.
Trifunctional
Ethoxylated(10)trimethylolpropane triacrylate, ethoxylated (9)trimethylolpropane triacrylate (SR 502), propoxylated(3)trimethylolpropane triacrylate, ethoxylated(6)trimethylolpropane triacrylate, propoxylated(6)trimethylolpropane triacrylate, propoxylated(3) glyceryl triacrylate, propoxylated(15)glyceryl triacrylate, ethoxylated(15)trimethylolpropane triacrylate.
Tetrafunctional or Higher
Ethoxylated(4)pentaerythritol tetraacrylate.
Monofunctional
Styrene, 4-styrenesulfonic acid, sodium styrene sulfonate, chloromethyl styrene, bromostyrene, vinyl pyridine, vinyl imidazole, vinyl acetate, vinyl neodecanoate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl methacrylate, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid.
Difunctional
Ethylene glycol dimethacrylate, 1,3-butyleneglycol diacrylate, di(ethyleneglycol) diacrylate, di(ethyleneglycol) dimethacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated(3)bisphenol-A acrylate, cyclohexanedimethanoldimethacrylate, 1,4 butandiol diacrylate, 1,6-hexanediol diacrylate, cyclohexanedimethanonol diacrylate, di(propylene glycol) diacrylate, ethoxylated(4)bisphenol- A dimethacrylate.
Trifunctional
Trimethylol propane trimethacrylate, trimethylol propane triacrylate, tris(2-hydroxy ethyl)isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated(3)trimethylolpropane triacrylate (PHOTOMER 4095).
Tetrafunctional or Higher
pentaerythritol tetraacrylate (PETA K), dipentaerythritol pentaacrylate, di-trimethylolpropane tetraacrylate, pentaacrylate ester.
In addition to the foregoing reactive diluent monomers, proprietary monomers such as the SR monomers available from Sartomer, Exton, Pennsylvania, the GENOMER line of monomers available from Rahn, Zurich, Switzerland, the PHOTOMER line of monomers available from Henkel Corporation, La Grange, Illinois or the UV-curable diluents available from Croda, Kent, United Kingdom, may also be utilized in the compositions of the present invention, provided, of course, that the Tg of the homopolymer of the candidate proprietary reactive diluent monomer falls within one or the other of the two classes of reactive diluents of the invention.
Acrylated urethanes are polyurethanes which have been treated so that acrylic or methacrylic functionalities are attached. They may have from 1 to 10 acrylic or methacrylic functionalities; however, for purposes of the present invention, 2 to 5 such functionalities are preferred and 3 functionalities is most preferred. Such acrylated urethanes are commercially available from Sartomer, Croda, Rahn, UCB Radcure (EBECRYL) and other suppliers of UV-curable materials. The specific molecular structures of commercially available acrylated urethanes are often proprietary but, for purposes of the present invention, those which are substantially aliphatic in nature are generally preferred.
The coating compositions of the present invention are, of course, cured to the finished dry coating after application to a substrate. Where electron beam curing of the applied coating is to be accomplished no initiator is required. However, where UV or visible light curing is to be utilized, or when the coatings are to be cured thermally, a suitable photoinitiator, thermal initiator or a compatible combination of photo- and thermal initiators is incorporated into the composition prior to coating thereof onto the substrate. Generally speaking, such initiators are to be utilized in amounts ranging from about 0.5 to about 5% by weight of the total composition.
Suitable thermal initiators for the coating compositions of the invention include peroxy or diazo compounds. Exemplary suitable peroxy compound initiators include methyl ethyl ketone peroxide, 2,4-pentanedione peroxide, methyl isobutyl ketone peroxide, dibenzoylperoxide, t-butyl peroxyneodecanoate, t-amyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-butyl peroxy-2,5,5-trimethylhexanoate, t-butyl peroxy-2-methylbenzoate, t-butylperoxyisopropyl carbonate, 1,1-di-(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di-(t-butylperoxy)cyclohexane, 2,2-di-t-butylperoxybutane, n-butyl-4,4-di(t-butylperoxy)valerate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-(2-t-butylperoxyisopropyl)benzene, dicumylperoxide, di-t-butylperoxide, di-(t-butylcyclohexyl)peroxydicarbonate, di-(2-ethylhexyl)peroxydicarbonate, cumylhydroperoxide, diisobutyryl peroxide, cumylperoxyneodecanoate, 2,4,4-trimethylpentyl-2-peroxyneodecanoate, t-amylperoxyneodecanoate, di-(s-butyl)peroxydicarbonate, t-butyl peroxyneodecanoate, di-(4-t-butylcyclohexyl)peroxydicarbonate, di-(2-ethylhexyl)peroxydiacronate, dimyristyl peroxydicarbonate, t-amyl peroxypivalate, t-butyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, 1,1,-di-(t-butylperoxy)cyclohexane, 2,2-bis 4,4-di(t-butylperoxycyclohexyl)propane , t-butyl peroxy-2-methylbenzoate, 2,2,-di(t-butylperoxy)butane, di-t-butyl diperoxyazelate, t-butylperoxy isopropyl carbonate, t-amyl peroxybenzoate, t-butyl peroxybenzoate di-t-butyl diperoxyphthalate, di-(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,4-di-(2-t-butylperoxyisopropyl)benzene, t-butylcumylperoxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hex-3-yne, di-t-butylperoxide, 2,4,4-trimethylpentyl-2 hydroperoxide, diisopropylbenzene monhydroperoxide, cumyl hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, diacetyl peroxydicarbonate, dioctanoyl peroxide, didecanoyl peroxide, t-butyl peroxydiethylacetate, t-butyl peroxyisobutyrate, t-amyl peroxyacetate, t-amylperoxy-2-ethylhexylcarbonate, t-butylperoxystearylcarbonate, t-butyl-3-isopropenylcumylperoxide, di-t-amylperoxide, di-(1-hydroxycyclohexyl)peroxide, 3,4-dimethyl-3,4-diphenylhexane. Peroxy initiators are available from, for instance, Akzo-Nobel Chemicals, Inc., Chicago, Ill.
Exemplary suitable azo compound initiators include 2,2xe2x80x2azobis(4-methoxy-2,4-dimethylvaleronitrile, 2,2xe2x80x2-azobis(2,4,-dimethylvaleronitrile, 2,2xe2x80x2-azobisisobutyronitrile, dimethyl-2,2xe2x80x2-azobis(isobutyrate), 2,2xe2x80x2-azobis(2-methylbutyronitrile), 1,1xe2x80x2-azobis(l-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyronitrile, 2,2xe2x80x2-azobis(2,4,4-trimethylpentane). Azo initiators are available from, for instance, E.I. DuPont VAZO Division, Wilmington, Del. and Wako Chemicals, Richmond, Va.
Exemplary suitable photoinitiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, p,pxe2x80x2-dichlorobenzophenone, p,pxe2x80x2-bisdiethylaminobenzophenone, Michler""s ketone, benzoinmethylether, benzoinethylether, benzoinisopropylether, benzoin-n-propyl ether, benzoinisobutylether, benzoin-n-butyl-ether, benzylmethylketal, tetramethylthiuram-monosulphide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoinperoxide, di-tert-butylperoxide, p-isopropyl-alpha-hydroxyiosbutylphenone, alpha-hydroxyisobutylphenone, dibenzosuberone, diethylthioxanthone, 2,2,-dimethoxy-2-phenyl acetophenone and the like. The photoinitiators used in the examples include DAROCURE 1173 (Ciba-Geigy Corp., Ardsley, Pa.) whose chemical name is 2-hydroxy-2-methyl-1-phenyl-1-propanone, CHIVACURE 173 (ChivaChem) having the same chemical structure and IRGACURE 369 (Ciba-Geigy Corp.) whose chemical name is 2-benzyl-2-dimethylamino-1-(4-morpholino) butanone-1. Any combination of these or other photoinitiators may be used to optimize the efficiency of curing with different light sources whose spectral ouputs may differ.
The coating compositions of the invention may also include various additives, including colorants and pigments, which are conventionally employed in coating compositions to confer or enhance various properties thereof. Such additives can, for instance, impart color, enhance wetting of substrates, impart mar or scratch resistance, control flow and leveling properties before curing, defoam, flat or function as fillers. Typically, such additives are employed in amounts of up to about 2% by weight of the total coating composition. Where the coating composition is earmarked for cure by light energy, such as by ultraviolet light curing thereof, those additives which opacify the coating film should, of course, be avoided. A number of exemplary additives which have been found to be useful in the coating compositions of the invention are set forth in the following table.
The nitrocellulose based coating compositions of the invention are applied to a substrate in any conventional manner so as to produce a film over the substrate and the resulting film then cured. The application can be achieved, for instance, by such techniques as spraying, doctor blading, brushing, sponging or even by dipping of the substrate into the composition followed by draining of the so wetted substrate.
In the working examples hereof the test substrates were maple or oak veneer panels which are representative of typical wood substrates for residential, commercial and gym flooring as well as for furniture and kitchen cabints. The panels were tested in both the pre-stained and natural condition, the test results being similar for each. In the case of pre-stained panels, MINWAX Golden Oak stain (Minwax Company, Inc., Upper Saddle River, N.J.) was liberally applied to the veneer surface of the panel, the excess stain wiped off and the thusly stained panel allowed to dry for approximately 16 hours at ambient conditions prior to the application of a sealer. The sealer employed was a photo-curable composition consisting of the following ingredients:
The sealer was applied to the panels and cured under a Fusion UV Systems, Inc. (Gaithersberg, Md.) H+ bulb at a panel feed rate of 20 feet per minute. The sealed panels were then lightly sanded with 220 grit non-stearated sandpaper and the so sanded panels then dedusted with a tack cloth. The test topcoat formulations of Examples 1 through 3 and 5 through 8 were then applied at a wet thickness of from about 25 to about 50 microns and the thusly applied wet films UV cured under the same conditions as set forth above with respect to the sealer. Testing of the cured films was undertaken shortly after completion of the curing step, often within 5 to 10 minutes thereof.